Treating hydrocarbons



.April 12, 1932. I H. T. DARLINGTON i" I m IIllI I I II Filed Nov. 24,1926 Patented Apr. 12, 1932 UNITED A STATES PATENT OFFICE HOMER T.DAR-LINGTON, OF WEST CHESTER, PENNSYLVANIA, ASSIGNOR TO MARTIN B.SCHUSTER, TRUSTEE, OF JOLIET, ILLINOIS TREATING HYDROGARBON SApplication filed November 24, 1926. Serial No. 150,630.

My invention relates to a method of treating liquid hydrocarbon for thepurpose of promoting cracking and the production of the lighterdistillates, particularly gasoline, or for the purpose of lightening thequality, and reducing the viscosity of the hydrocarbon, or for otherwisebeneficially influencing and promoting the cracking operation in wayswhich will more fully appear from the following specification.

In carrying out the art of my invention, I

- bring together hydrocarbon and ordinary salt, alum, sodium-sulphate,aluminum-chloride (dissolved in water), or other chemical salts, or -anycombination of one or more of them, in aqueous or other solution intohydrocarbon oil under conditions of temperature and pressure conduciveto cracking oil, in such a manner that on evaporation of the solventnamed above the agent is left as favorable colloid nuclei incorporatedor dispersed, or both, in the hydrocarbon being treated, bringing aboutcracking and changes favorable for the elimination of carbon as asuspension in the residue oil. Favorable conditions for the carrying outof the present process are the following, to-wit: a temperature above450 F., but preferably in practice between 750 F. and 1000 F., and apressure sufficient to keep the hydrocarbons which are heavier thangasoline liquid at the temperature used, said pressures ordinarilyrunning between 100 pounds and 1500 pounds to the square inch.

I find it favorable to emulsify. or homogenize the salt solution in oiland spray the emulsion into the hot chamber; for instance, into a gasspace above the oil in a reaction chamber or a cracking still, or sprayas above through gas into hot oil, or force it directly into the hotoil, preferably through an insulated nozzle, or to bring together hotoil from the cracking still with the oil emulsion, in which cases theevaporation of the solvent leaves the salts in a dispersed orincorporated form which for practical purposes is equivalent or nearlyso to a colloidal dispersion or incorporation, though not necessarilychemically so, where, upon acting as an aid in cracking, the nucleisalts become coated with carbon and can be removed from the stillcontinually or intermittently.

shown in the accompanying drawings, in WhlCll- Figure 1 is adiagrammatic view showing the apparatus in vertical section;

Fig. 2 is an enlarged partial vertical section of the spray nozzle shownin Fig. 1; and

Fig. 3 is a similar view of a reaction chamber similar to that of Fig. 1showing a modified form of the spray device.

In the embodiment illustrated, a reaction chamber 10 is heated by meansof a pipe coil 11 through which oil is circulated by means of a pump P,the oil 11 being heated in a well known manner by means of a suitablefurnace 12. Fresh oil may be introduced into the system through a pipe13. A suitable dephlegmator or the like 14 connects with the top of thereaction chamber above the normal level of the oil therein, and iscontrolled by means of a valve 15. Vapors, as gasoline or the like,passing the valve 15 are condensed in suitable condensing coils 16 whichare cooled in a well known manner, the liquid as gasoline or the likebeing stored in a suitable tank 17. Residual oil is withdrawn preferablyfrom the bottom of the reaction chamber 10 through a draw-off pipe 18which is controlled by means of a valve 19.

The foregoing apparatus is well known in the oil cracking art. To this Ihave added a spray nozzle, which consists of an outer shell 20, to whichis supplied through a pipe 21 a suitable salt solution or the like, aswill hereinafter be described. For properly atomizing the liquid passingthe nozzle 20, I have provided a steam pipe 22 with steam suppliedthereto at a suitable pressure for prop- Apparatus for carrying out thisprocess is against the surface of the liquid in the reacdividedparticles which enter the oil and 4 tion chamber 10. Since this reactioncham:

her is maintained under conditions of temrature and superatmosphericpressure conucive to cracking, the temperature is sufiiciently high tocause the liquid solvent or ve hicle to become very quickly vaporized,thereb leaving the salt solid in the form of finely go into colloidaldispersion or suspension therein.

The nozzle 20 is so situated as to preclude the possibility of sprayingany of the liquid partlcles containing the salt directly against thewalls of the reaction chamber 10. In other words, the stream of theliquid particles is so directed as to cause, the liquid to be vaporizedbefore the particles can come in contact with a wall of the vessel. Inthis way, no deposition of the salt can be made upon the walls of thevessel, inasmuch as the salt or other solid being in colloidalsuspension in the oil will not adhere to the walls of the vessel, aswould be the case if the liquid solution were to be allowed to come incontact with the walls of the vessel before evaporation of the liquidsolvent or carrier took place.

In Fig. 3 is shown a modification of the construction in which thereaction chamber 10a is supplied with the same kinds of salts or othersolids for solution or suspension in liquid through a spray nozzle 24,which is located beneath the surface of the hydrocarbon oil to betreated and preferably near the bottom. This nozzle is preferablysurrounded with a suitable heat insulating covering 25, the effect ofwhich is to prevent evaporation, to a large extent at least, of theliquid solvent or vehicle. If desired, the nozzle 20 of Figs. 1 and 2may also be provided with an insulating covering for the same reason;

namely, to prevent the deposition of solids within the nozzle due toevaporation of the liquid solvent 'or vehicle.

In the form shown in Fig. 3 steam may be added, if desired, but thedevice will operate quite effectually if the nozzle is supplied onlywith a salt solution or with a solid in suspension in a liquid undersuflicient pressure to cause it to be forced into the reaction chamberagainst the pressure therein, and also sufficient to prevent clogging ofthe nozzle due to the deposition of the solute or other solid which iscarried thereby.

This liquid solvent or carrier preferably asauua action chamber istreated, so that when this liquid material is injected into the reactionchamber through either the nozzle 20 or the nozzle 24, the liquidsolvent or vehicle will rapidly be evaporated leaving the solid behindin the hydrocarbon oil. When this liquid material is injected throughthe nozzle 24 the steam orvapor thus formed in the hot oil causes thesolid particles, which are simultaneously formed, to be separated fromeach other in a finely divided state of colloidal dispersion in the hotoil. At the same time. the steam or ve or of the liquid thus generatedassists great y in removing the vapors-of gasoline and other lighthydrocarbons from the oil through which they rise.

The discrete solid particles thus dispersed throughout the body of oilunder treatment act as nuclei for the deposition of carbon, and at thesame time provide surfaces where cracking of the oil can readily occur,the deposition of carbon being an incident to the cracking of the oil.As this carbon continues to be deposited upon these solid particles, itwill no longer remain in suspension, unless agitated, but sinks and isdrawn ofi from the body of the oil, either continuously orintermittently through the pipe 18, fresh cracking stock being suppliedthrough the pipe 13 and fresh solid particles are supplied to the oilthrough the nozzles 20 or 24, so as to maintain the level of the oilsubstantially constant.

I have found that when'salts are favorable to the production ofcracking, deposition of carbon, decolorizing, or other purposes, I amenabled to get the maximum amount of efficiency by bringing them to thesmallest size possible, and that by putting them in solution andtreating them in the manner described, these particles do not againcoalesce, but are held separate from each other and expose the largestpossible surface for effective use to the desired end.

Attention is called to the fact that in the past, particularly indistillin oils containing salt water have brought a out expensiveoperating conditions, as the salt has crystallized on the sides ofthestills, forming an objectionable coating. I obviate this trouble bybringing such oils containing natural salt or chemical salts insuspension or dispersion, directly into the presence of hot oil, andcommingling and incorporating them therewith, at a temperature andpressure suflicient to almost immediately evaporate the water or othersolvent, thus leaving the salt or salts in a dispersed or incorporatedform, accomplishing by means of my discovery a favorable way ofinfluencing the treatment of oils under conditions of heat and pressureconducive to cracking. The solution should be added sufiiciently farfrom the sides of the apparatus and commingled with the hydrocarbontherethe sprinklers 28, by means of a pump (not shown) which isdisposed'between the pipes 33 and 34 which are respectively connected tothe trough and the sprinklers. The water passes from the sprinklers downthrough the screens 29, bein cooled in its downward path, as in usualpractice by the passage of air through the tower. The cooling waterfalls over the perforated distributin pan 31 and'is distributed over thetubes of changer tube unit 30, passing on to thecollecting trough 32,whereupon the cycle is repeated. In the cooling tower illustrated, fourheat exchanger tube units are employed, the fluid to be cooled beingcirculated through the units and the bowing of the tubes for the purposeof removing deposits therefrom being eflected when desired, as describedwith reference to Figs. 1 to 5.

In Fig. 8 there is illustrated an application of the. heat exchangertube unit of this in-' vention to a standard type of evaporator. Theevaporator comprises an outer shell indicated generally by, the numeral40, which shell is provided with inlet ports 41 and outlet port 42. Theheat exchanger tube unit is horizontally disposedwithin the shell 40, anopening 43 being provided in one end of the shell through which the tubeunit is inserted and removed. A flanged collar 44 is provided around theperiphery of the opening 43. The periphery of the tube sheet 45 at the,

outer end of the tube unit, is adjacent the flanged collar 44. In thisconstruction of the tube unit, modified forms of heads are employed. Thehead 46 comprises a dome shaped casting having a transverse wall 47formed therein, dividing the'head'into relatively large and smallrespective upper and lower compartments. An inlet port 48 is provided inthe upper compartment and an outlet port 49 is provided in the lowercompartment. The head 46, tube sheet 45 and collar 44 are securedtogether by bolts not shown. At the opposite end of the tube unit a domeshapedhead' 50 is provided. The head'50 is formedwith a peripheralflange 51 and is secured to the tube sheet 52 by bolts not shown. Acompartment is thus provided at this end of the unit into which all ofthe tubes open. This end of the unit is free for longitudinal motion asthe tubes expandor contract. Transverse beams 53 and 54 are provided forsupporting the unit while permitting the same to slide longitudinallythereon. A port 55 having a suitable removable cover 56 is provided inthe lower portion of the tank, as in usual practice, for removingdeposits and affording access to the interior of the shell.

In the operation of the vaporizer, heating fluid is introduced to theexchanger tube unit through the port 48 and passes through the tubes insubstantially the same manner as described with reference to the formerstruceat ex-' the heating fluid while at its highest temperature wlll bepassing through the tubes toward the head 50, and while at its lowesttem? perature'will be passing back toward. the head 46, and thus thefluid while at a high temperature will be passin through a greaternumber of tubes than vihile at a lowered one, thereby effecting thegreatest possible heat exchange. Liquid to be vaporized is introducedinto the shell through the inlet ports 41 where it circulates around thetubes 3, and vapor which is formed by the exchange of heat, passes outthrough the outlet'port 42. Bowing of the tubes for the purpose ofremovin deposit formed thereon may be effected either by introducingsteam into the tubes, through the opening 48 or by simply varying thetemperature of the heating fluid passed therethrough. When desired aseparate port, similar to port 21, may be formed in the head 46 forseparately introducing steam.

While there. has been hereinbefore described specific embodimentsof theinstant invention it will be understood that many and various changesand modifications in form, procedure, details of construction and aplications of the invention may be made w1th-- o'ut departing from thespirit of the invention, and it will be'understood that all and any suchchanges and modifications as fall within the scope of the appendedclaims are contemplated and are to be considered as a part of theinstant invention. L

What we claim as new and desire to secure by Letters Patent is: i

1. In a heat exchanger, the combination of a straight tube, adapted forthe circulation of fluid therethrough; and means for automaticallyeffecting curvature of said tube when the same is elongated by theapplication of heat thereto.

2. In a heat exchanger, the combination of a plurality of straight,parallel, spaced tubes, adapted for the circulation of fluidtherethrough; and means operatively connected to said tubes forautomatically effecting curvature of the same when said tubes areelongated by the application of heat thereto. 3. In a heat exchanger,the combination of a normally straight tube adapted for the circulationof fluid therethrough; bending means adjacent said tube normally held inan angular position; means connecting said tubes and said bending meansat the respective ends thereof; and means operatively connecting saidtube with said bending means between said respective ends, whereby saidbending means will be moved from angular position to straight lineposition and will eflect a curvature of said tubes when the same betweensaid tubes and said bending means atthe respective ends thereof; andmeans op-' eratively connecting said tubes with said bendingmeansbetween the said respective ends,- whereby said bending. means willbe moved from angular to straight line position and will effect acurvature of said tubes when elongation of said tubes is caused by theapplication of heat thereto.

5. In a heat exchanger, the combination of a plurality of normally,straight tubes, adapted for the circulation of fluid therethrough; atubeplate at each of the opposite ends of said tubes securing thesame intheir relative positions; tie members secured to said tube plates saidtie membersbeing normally held in angular positions; and'means disposedbetween the said tube plates. operatively connecting said tubes and saidtie members, whereby upon elongation of said tubes caused by theapplication of heat thereto. said tube plates will be moved outwardlyefiecting a straightening of said tie members and causing curvature ofsaid tubes,.and whereby said tube lation,

plates willbe heldin fixed spaced relation when said-tie members havereached straight line positions and further elongation of said tubeswill effect further curvature of the same while their ends are held infixed spaced re- '6. In a, heat exchanger, the combination of aplurality of spaced. parallel, normally straight tubes; compartmentsdisposed at the opposite ends of said tubes,adapting the same for thecirculation of fluid therethrough, each fr'd t t.co"r" tb lt-,, 0 gmcompar men q mp 15mg a u a e =will be moved outwardly to efiect thestraighton its innerend in which the ends of said tubes are secured, asubstantially box shaped bodyportion, and a cover disposed over itsouter end, tie members having ends secured in said compartments andnormally held in angular positions; and means. disposed betweenthe tubeplates, operatively connecting the tubes and tie members, whereby uponelongation of said tubes, caused by the application of heat thereto,said tube'plates will be moved outwardly to effect they straightening ofsaid tie members from their angular -posi-.

tions and curvature of said tubes will be effected.

7 In a heat exchanger, the combination of a plurality of spaced,parallel, normally straight tubes'adapted for the circulation of fluidtherethrough; a tube plate disposed at each ofthe opposite ends of saidtubes securing the same in "their relative positions; a

angular: positions and guide plate disposedbetween said tube plates I Ostraightening of said tie' members from their curvature of said tubes In'a'heat 'exchanger, the combination of a-normally straight tube adaptedfor the circulation- -offluidtherethrough; tying means adj accentv saidtube normally held in an connecting means will-be moved apart and saidangular tying means will be moved to a straight line position effectinga curvature of said tubes. v

9. In a heat exchanger, the combination of a-pluralit of spaced,parallel, normally straight tu es; tube plates disposed at the oppositeends ofsaid, tubes holding the same in their relative positions; aplurality of tie members connected to said tube plates and normally heldin angular positions; and means disposed between said tube platesconnecting said tie members with said tubes whereby upon elongation ofsaid tubes b the application of heat thereto, said tube p ates relativespaced positions; tie members for each group-of tubes connected to thetube plates and normally held in angular positions; and means for eachgroup of tubes operatively connecting its said guide member and said tiemember, whereby upon elongationof said tubes by the application of heatthereto, said tube plates will be moved apart and said tie members willbe moved to straight line positions and curvature of said tubes will beefi'ected thereby.

11. In a heat exchanger, the combination of a plurality of groups ofparallel, spaced, normally straight tubes; a tube plate disposed at eachof the'opposite ends of said tubes, securing the same in their relativepositions; a guide plate for the tubes of each of said groups, saidguide plate havinga. plurality of orifices formed therein through whichsaid tubes are passed; tie members for each group of tubes connectedwith said tube plates, said tie members having hinged concentralportions of said tubes, whereby upon elongatlon of said tubes, by theapplication of heat thereto, said head members will be moved apart andsaid tie members will be moved to straight line position efiecting thecurvature of said tubes, and said divided head member havin a steam portformed therein for the intro notion of steam into the same.-

GEORGE T. JACOCKS.

JOHN L. KRIEG.

nections adjacent said guide plates and being normally held in angularpositions; and means on said guide plates operatively connecting thesame to the tie members of their respective groups, whereby uponelongation of said tubes by the application of heat thereto, said tubeplates will be outwardly moved and said tie members will be moved tostraight line positions, effecting the curvature of said tubes.

12. In a heat exchanger, the combination of a plurality of spaced,parallel, normally straight tubes; substantially box shaped head membersdisposed at the opposite ends of said tubes having tube plates on theirinner sides, said tube plates holding the ends of said tubes in theirrelative positions, and said head members having cover plates disposedon their outer sides, one of said head members having a transverse wallformed therein dividin the interior of same into two sections, an aninlet port formed in one section of said head member and an outlet portformed inv theother section, whereby a fluid may be circulated throughsaid head members and 7 tubes; and tie members secured to said tubeplates normally held in an angular position and operatively connected tothe central portions of said tubes, whereby upon elongation of saidtubes by the application of heat thereto, said head members will bemoved apart and said tie members will be moved to straight line positioneffecting thecurvature of said tubes.

13. In a heat exchanger, the combination of a plurality of spaced,parallel, normally straight tubes; substantially box shaped head membersdisposed at the opposite ends of said tubes, havlng tube plates securedon their inner sides, said tube plates holding the ends of the tubes intheir relative positions, and said head members having cover latesdisposed on their outer sides, one of sai headmembers having atransverse wall formed therein dividing the interior of same into twosections, and an inlet porttformed in one section of said head memberand an outlet port .formed in the other section, whereby fluid may becirculated through said head members and tubes; and tie members securedto said tube plates normally held in an angular position and operativelyconnected-to the

